Reactive arylazo-pyrazolone dyestuffs

ABSTRACT

Dyestuff of the formula   WHEREIN D is the residue of a diazo component; A, B and Z are substituent moieties; m and n are integers and R is a hydrocarbon bridging member as well as the copper, cobalt and chromium metal complexes thereof, which are useful for dyeing wool, polyamide, silk or cellulose fibers in good dye yields having highly brilliant greenish to reddish yellow shados possessing good fastness properties.

Ullltfld States Patent [1 1 3,718,641 Muller et al. 1 Feb. 27, 1973 REACTIVE ARYLAZO-PYRAZOLONE [56] References Cited DYESTUFFS UNITED STATES PATENTS 1 lnvemrs= Muller, Frankfurt am Main; 3,435,023 3/1969 Meiningeretal. ..260/l63 Hanswilli von Brachel, Offenbach am Main; Rudolf Klein, Frankfurt Primary Examiner-Floyd D. Higel am Main-Fechenheim; Ewald A -C nolly & Hutz Schmidt, Bischofsheim; Heinz Bender, Bergen-Enkheim, all of [57] ABSTRACT Germany Dyestuff of the formula [73] Assigneez Casseliii F arlii verke Mainkur D N=N IF Frankfurt, Germany H0 N [22] Filed: May 4, 1970 I 21 Appl. No.: 34,604 A H E (Antjqq- R-S0z-Z [30] Foreign Application Priority Data (mm May 6, 1969 Germany ..P 19 22 940.4 wherein D is the residue of a diazo component; A, B and Z are substituent moieties; m and n are integers [52] U.S. Cl. ..260/l62, 8/50, 8/51, and R is hydrocarbo" bridging member as as 260/147 260/153260/154 260/158 the copper, cobalt and chromium metal complexes 260/160, 260/163 thereof, which are useful for dyeing wool, polyamide, silk or cellulose fibers in good dye yields having highly 51 m. Cl. ..C09b 62/70, c091) 62/82 brilliant greenish F Shad Imssessing 581 Field of Search ..260/l62, 163, 147 fasmess PmPemes- 7 Claims, No Drawings REACTIVE ARYLAZO-PYRAZOLONE DYESTUFFS The present invention relates to azo dyestuffs of the pyrazolone series of the general formula atoms, phenylene, cyclohexylene, endomethylenecyclohexylene or endoethylenecyclohexylene.

as well as the metal complexes of these dyestuffs.

Those dyestuffs wherein n and m are one, the substituent A is in the 2-position, the substituent B is in the 3-position and the acylamino group is in the 5-position of the phenyl nucleus of the azo component are particularly preferred.

The preferred diazo components of the present invention include those of the aminobenzene, aminonaphthalene, aminodiphenyl, aminoazobenzene, aminophenylazonaphthalene, aminothiazole and the aminobenzthiazole series. Particularly preferred D moieties embrace phenyl, naphthyl, diphenylene, azophenyl, phenyleneazonaphthalene, thiazolyl, benzthiazolyl and said radicals having one or more substituents selected from the group consisting of SO l-l, COOH, chloro, bromo, hydroxy, alkyl containing one to four carbon atoms, alkoxy containing one to four carbon atoms, nitro, acetylamino, B- chloropropionylamino, acetylalkylamino containing three to six carbon atoms, chloro-l ,3,5-triazinylamino, 2,3-dichloro-quinoxaline-6-carboxylamino, trichloropyrimidinylamino and fl-sulfatoethylsulfonyl.

Typical examples of the diazo components according to the present invention include: aminobenzenes, aminobenzene sulfonic acids, aminobenzene disulfonic acids, aminobenzene carboxylic acids, aminobenzene dicarboxylic acids, aminobenzene sulfonic acid carboxylic acids, aminophenol sulfonic acid, aminonaphthalenesulfonic acids, aminonaphthalene disulfonic acids, aminonaphthalene trisulfonic acids, aminonaphthol sulfonic acids, aminonaphthalene carboxylic acids, aminonaphthalene sulfonic acid carboxylic acids, aminodiphenyl sulfonic acids, aminodiphenyl carboxylic acids, aminodiphenyl disulfonic acids, aminoazobenzene sulfonic acids, aminoazobenzene carboxylic acids, aminophenylazonaphthalene sulfonic acids, aminobenzthiazole as well as aminobenzthiazole sulfonic acids. These components may also bear substituents customary in the azo chemistry, such as domethylenecyclohexylene chlorine, bromine, hydroxy, alkyl containing one to four carbon atoms, alkoxy containing one to four carbon atoms, nitro, acetylamino, B- chloropropionylamino, acetylalkylamino containing from three to six carbon atoms or chloro-l,3,5- triazinylamino, 2,3-dichloro-quinoxaline--carboxylamino, trichloropyrimidinylamino.

Further typical diazo components are those bearing an additional reactive residue, such as 4-aminophenyl- B-sulfatoethylsulfone, 3-aminophenyl-B-sulfatoethylsulfone, 2-methoxy-4-amino-phenyl-B-sulfatoethylsulfone, 2-sulfo-4-aminophenyl-B -sulfatoethylsulfone as well as the condensation products prepared from aromatic diamines and derivatives, for instance, acid chlorides, of those acids containing themselves an additional residue capable of reacting with the fibers, such as the condensation product made from 1,4-phenylenediamine-Z-sulfonic acid and cyanuric chloride, the condensation product made from 1,3-phenylene-diamine- 4-sulfonic acid and acrylic acid chloride or the condensation product made from l,4-phenylene-diamine-2,5- disulfonic acid and B-chloroethylsulfonyl-endomethylenecyclo-hexane-carboxylic acid chloride.

Further typical diazo components are those bearing themselves an azo group, such as 2-(4'-aminophenyl)- azo-naphthalene-4,6,8-trisulfonic acid or 2-(2'-methyl- 4'-aminophenyl)-azo-naphthalene-3,6,8-trisulfonic acid.

The residue R may be, for instance, the ethylene, butylene, phenylene, cyclohexylene, enor the endoethylenecyclohexylene residue.

The dyestufis of the present invention are obtained by reacting dyestuffs of the general formula DN=N coon 1 1r HO N or, if the residue of the diazo component D bears in the o-position to the azo bridge a group capable of forming a complex salt, the metal complexes of these dyestufis with reactive derivatives of an acid of the general formula 5 ties.

As compared with the dyestuffs described in German document laid open to public inspection No.

1,066,302, Example 1, which contains instead of the residue of the acid 111 the residue of the cyanuric chloride, as well as compared with the dyestuff described in German document laid open to public inspection No. 1,111,753, Example 15, which contains the residue of the fi-chloropropionic acid as reactive component, the dyestuffs of the present invention have the advantage of being universally applicable according to the two-step-process.

Unlike the corresponding dyestufis of British specification No. 1,144,966 (page 13, table 2) the dyestuffs of the present invention distinguish themselves by a greater brilliancy. Moreover, their preparation requires a substantially smaller excess of acylating agents.

The following examples are given for the purpose of illustrating the present invention. All temperatures are given in degrees centigrade.

EXAMPLE 1 a. 221 g. aniline-2,5-disulfonic acid are diazotized in the usual manner and coupled onto 233 g. 1-(2- methyl- -aminophenyl )-pyrazolone-3-carboxylic acid. The thusly obtained dyestuff is separated by salting out or acidify-ing to a pH-value of 2 and isolated as usual. The dyestuff is again dissolved neutral by the addition of 9000 c.c. water, admixed with 92 g. sodium bicarbonate and acylated at l0-15 with 312 g. B chloroethylsulfonyl-endomethylene-cyclohexane-carboxylic acid chloride (preparation according to British Patent specification No. 1,144,966, Example 1). If the dyestuff is no longer diazotizable, it is precipitated by the addition of potassium chloride and vacuum-dried at 60.

b. Cotton yarn is dyed at 40 during 1 hour with 2 percent of the dyestuff, 40 g./l. Glaubers salt and g./l. calcined sodium carbonate at a liquor ratio of 1:20. Obtained is a yellow dye-ing having a good fastness to light.

Equally valuable reactive dyes are obtained if the diazo and coupling components enumerated in the following table are employed whereas apart from that the working is carried out as described hereinbefore.

disulfonic acid 2-naphthylamine-3,6,8- trisulfonic acid pheny1)-pyrazolone-3- carboxyltc acid l-(2 '-methoxy-5 '-aminophenyl)-pyrazolone-3- carboxylic acid 4-aminoaninole-3- l-(2'-mcthoxy-5-aminocarboxylic acid EXAMPLE 2 a. 173 g. aniline-o-sulfonic acid are diazotized in the usual manner and coupled at a pH value of 5-6 onto 331 g. l-(2-methyl-3 '-sulfo-5 '-aminophenyl)- pyrazolone-3-carboxylic acid. At a pl-l-value of l the dyestuff is separated and dissolved in 3000 c.c. water at a pH value adjusted to 7,5 by the addition of aqueous sodium hydroxide solution. First g. sodium bicarbonate and then 330 g. B-chloroethylsulfonylcyclohexane-carboxylic acid chloride dissolved in 300 g. ethylene chloride are added. Stirring is continued until there are only tracec of the initial dyestuff detectable in the chromatogram. Subsequently, the dyestuff is precipitated with common salt and vacuumdried at 60.

b. A fabric on the basis of regenerated cellulose is printed with the following printing paste:

50 g. of the dye obtained as described a ve 100 g. urea 390 g. hot water 450 g. alginate thickener 10 g. sodium-m-nitrobenzenesulfonate 1,000 g. TOTAL After printing and drying the fabric is padded with 30 g. aqueous sodium hydroxide solution of 38Be 150 g. soda 50 g. potassium carbonate 100 g. common salt water 1000 g. TOTAL the alkaline agent. For instance a fabric on the basis of alkalized or mercerized cotton is printed with the following printing paste:

50 g. of the dye obtained as described above 50 g. urea 410 g. hot water 450 g. alginate thickener 30 g. sodium bicarbonate 10 g. sodium-m-nitrobenzenesulfonate.

After printing and drying the fabric is steamed for approx. 5 minutes at l00-l 05, rinsed and washed.

A similar result is obtained if the fixation is performed by dry-heating, for instance, during 5 minutes at -l50.

Equally valuable dyes are obtained if instead of the above-mentioned acid chloride the following compounds are employed:

B-chloroethylsulfonyl-endomethylenecyclohexanecarboxylic acid chloride,

B-chloroethylsulfonyl-endoethylenecyclohexanecarboxylic acid chloride,

4-B-chloroethylsulfonyl benzoyl chloride,

3-B-chloroethylsulfonyl benzoyl chloride,

Z-B-chloroethylsulfonyl benzoyl chloride,

3-fi-chloroethylsulfonyl butyroyl chloride,

y-vinylsulfonyl butyroyl chloride,

B-bromoethylsulfonyl-endomethylenecyclohexanecarboxylic acid bromide.

EXAMPLE 3 525 g. of the azo dyestuff made from diazotized 2- aminophenol-4-sulfonic acid and l-(2'-ethyl-3'-amino- 5'-sulfophenyl)-pyrazolone-3-carboxylic acid are converted in the usual manner into the copper complex. At a p value of 7,2 the complex being formed is dissolved in 2,5 1 water, admixed with 200 g. sodium bicarbonate and 347 g. 3-B-chloroethylsulfonylbenzoyl chloride, dissolved in 700 cc acetone, and stirred until the dyestuff is no longer diazotizable. Subsequently, it is precipitated by the addition of potassium chloride and vacuum-dried at 65. Obtained is a yellowish brown dyestuff having good fastness properties.

The following table indicates further components yielding valuable dyes if they are employed according to the above Example:

Heavy Shade Diazo Component Azo Component Metal on cotton Laminophenol-S- sulfonic acid l-(2'-methyl-5'-amino-phenyl)- pyrazolone-B-carboxylic acid reddish brown 2-aminophenol-4,6- disulfonic acid l-(2-chloro-3'-amino-5- sulfophenyl)-p razolone-B- carboxylic aci C 2-naphthylamine-4,8-

disult'onic acid l-(2'-ethoxy-3'-sulfo-5- amino hen l azolone-3- carbmFylic eld brown (dyestuff subsequently coppered in the presence of 1 2) 2-(2'-methyl-4'-amino- 5-methoxy-phenyl)- azonaphtha-lene-4,8- diaulfonic acid l-(2'-methyl-3'-sulfo-5'- aminophenybzryrazol-one-iica'rboxylic aci violet (dyestuff subsequently coppered in the presence of CuSO.) l-amino-2-naphthol-4- sulfonic acid H 2' 6'-dimethyl-3'-aulfo-5 amino-phenyl)-pyrazolone-3- carboxylic acid brown 2-aminophenol-4- sulfonic acid l-(2',4',6'-tn'methyl-3 '-sulfo-5 aminophenynzryrazolonedcarboxylic aci reddish brown EXAMPLE 4 223 g. Z-naphthylamine-l-sulfonic acid are diazotized in the usual manner and coupled at a p value of 5-6 onto 329 g. l-(2-methoxy-3'-sulfo-5- aminophenyl)-pyrazolone-3-carboxylic acid. The dyestuff solution is adjusted to a p value of 7,5 admixed with l00 g. sodium bicarbonate and 1000 g. ethylene chloride and then stirred with 256 g. 3-{-]- chloroethylsulfonyl butyroyl chloride until the dye stuff is no longer diazotizable. Subsequently, it is precipitated by the addition of common salt and vacuum-dried at A fabric on the basis of alkalized or mercerized cotton is printed with the following printing paste:

50 g. of the dye obtained as described above g. urea 390 g. hot water 450 g. alginate thickener 10 g. sodium salt of the m-nitrobenzoylsulfonic acid.

After printing and drying the fabric is padded with 100 g. aqueous sodium hydroxide solution of 38Be g. soda 50 g. potassium carbonate 100 g. common salt water 1,000 g. TOTAL Shade Diazo Component Azo Component on Cotton 2-naphthylamine-5- l-(2'-methyl-3'-sulfoyellow sulfonic acid 5'-aminophenyl)-pyrazolone-3-carboxylic acid 2-naphthylamine-7- sulfonic acid Z-naphthylamine-l ,5- disulfonic acid 2-naphthylamine-3,6-

l-(2'-phenoxy-3'-aulfodisulfonic acid 5 '-aminophenyl)-pyrazolone- 3-carboxylic acid l-(2'- methoxy-3'-sulfo-5'- aminophenyl)-pyrazolone-3- carboxylic acid l-(2'-methoxy-3 '-sulfoyellow 5 '-aminophenyl)-pyrazolone- 3carboxylic acid 2-naphthylamine-5 ,7- disulfonic acid 2-naphthylamine-4.8- disulfonic acid 2-naphthylamine- 3,6,8trisulfonic acid pyrazolone-I! -carboxylic acid Z-naphthylamine- 4,6,8-trisulfonic acid 6-nitro-2-naphthylamine-4,8-disulfonic acid 6-acetamino2- naphtl1ylamine-4,8- disulfonic acid l-naphthylamine-Z- l-(2'-methyl-3'sulfo-5 aminophenyl)-pyrazolone- S-carboxylic acid sulfonic acid l-naphthylamine4- sulfonic acid l-naphthylamine-S- l-(Z '-ethoxy-3 '-sulfo-5 sulfonic acid aminophenyl)-pyrazolone- 3-carboxylic acid l -naphthylamine-6- sulfonic acid l-naphthylamine-8- sulfonic acid l-napthylamine-2,5- disulfonic acid l-naphthylamine-6,8- disulfonic acid l-na hthylamine2,4,7- trisu fonic acid l-naphthylamine-3 ,6,8- trisulfonic acid aniline o-toluidine p-bromoaniline 2,5-dichloroaniline p-anisidine aniline-Z-sulfonic acid aniline-3-sulfonic acid aniline-4-sulfonic acid aniline-2,5-disulfonic acid 4-chloroaniline-2- sulfonic acid 2-chloroanilinc-4- sulfonic acid 4-methoxyaniline-2- sulfonic acid 4-aminophenyl-B- sulfateethylsuli'one S-aminophenyl-B- sulfatoethylsulfone 2-methoxy-4- aminophen l- B-sulfatoethy sulfone 4-N-methyl-N- acetylaminoaniline-2-sulfonic acid 4-acetamino-aniline-2- sulfonic acid 3-8- chloropropionylaminoaniline-Z-sulfonic acid condensation product from p-phenylenediaminesulfonic acid, cyanuric chloride aminophenyl )-pyrazolone- S-carboxylic acid sulfophenyl )-pyrazolone-3 arboxylic acid l-(2 '-phenoxy-3'- amino- '-sulfophenyl)- pyrazolone-B-carboxylic acid l -(2 '-methyl-3 '-amino- 5 '-sulfophenyl)-pyrazolone- 3-carbonsaure 1-(2'-methoxy-3-amino- 5 '-sulfophenyl)-pyrazolone- 3-carboxylic acid l-(3'-methyl-2'-sulfo-S aminophenyl)-pyrazolone- B-carboxylic acid l-(2'-phenylamino-3'-sulfo yellow 5 '-ammophenyl)-pyraz,olone aminophenyl)-pyrazolone-3- carboxylic acid carboxyphenyl)-pyrazolone- 3-carboxylic acid 1-(2'-methoxy-3'-amino-5'- carboxyphenyl)-pyrazolone- S-carboxylic acid l-(2'-chloro-3'-carboxy-5'- aminophenyl)-pyrazolone-3- carboxylic acid l-(2'-methyl-3-sulfoyellow 5 '-aminophenyl)-pyrazolone- 3-carboxylic acid orange aminobenzthiazole 2-(2'-methyl-4'-aminomethoxyphenyl azonaphthalene- 4,8-disulfonic acid red 0 those of the formula DN=N COOH i t HO N and the copper, cobalt and chromium metal complexes thereof wherein D is selected from the group consisting of phenyl, naphthyl, diphenylene and said radicals having one or more substituents selected from the group consisting of -SO H, COOH, chloro, bromo, hydroxy, alkyl containing one to four carbon atoms, alkoxy containing one to four carbon atoms, nitro, acetylamino, B-chloropropionylamino, acetylalkylamino containing three to six carbon atoms and B- sulfatoethylsulfonyl; A is halogen, alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, phenylamino, phenoxy, substituted phenylamino or substituted phenoxy, said substituents being halogen or alkyl having one to four carbon atoms; B is -SO H or COOl-l;nis l, r 3; m is0 or l;m+n is an integer of from one to four and R is alkylene having 1 to 8 carbon atoms, phenylene, cyclohexylene, endomethylenecyclohexylene or endoethylenecyclohexylene and Z is vinyl or -CH --CH X wherein X is halogen or -SO -,l-l.

2. The dyestuff of claim 1 wherein n and m are each 1, A is a 2-position substituent, B is a 3-position substituent and is a S-position substituent.

3. The dyestuff of claim 1 wherein said D is substituted with COOH, -SO H or both of these moieties.

4. The dyestuff of claim 1 wherein n is 2,5-disulfophenyl, n is 1 and A is Z-methyl, m is zero, the acylamino group is a 5-position substituent, R is endomethylenecyclohexylene and Z is B-chloroethyl 5. The dyestuff of claim 1 wherein D is o-sulfo-phenyl, n and m are each 1, A is 2-methyl, B is 3-su1fo, the acylamino group is a S-position substituent, R is cyclohexylene and Z is B-chloroethyl.

6. The dyestuff of claim 1 wherein D is 3-sulfo-6- hydroxyphenyl, n and m are each 1, A is 2-ethyl, B is 5- sulfo, the acylamino group is a 3-position substituent, R is phenylene and Z is B-chloroethyl.

7. The dyestuff of claim 1 wherein D is 2-sulfonaphthyl, n and m are each 1, A is 2-methoxy, B is 3- sulfo, the acylamino group is a S-position substituent, R 65 is propylene and Z is fi-chloroethyl. 

2. The dyestuff of claim 1 wherein n and m are each 1, A is a 2-position substituent, B is a 3-position substituent and is a 5-position substituent.
 3. The dyestuff of claim 1 wherein said D is substituted with -COOH, -SO3H or both of these moieties.
 4. The dyestuff of claim 1 wherein D is 2,5-disulfophenyl, n is 1 and A is 2-methyl, m is zero, the acylamino group is a 5-position substituent, R is endomethylenecyclohexylene and Z is Beta -chloroethyl.
 5. The dyestuff of claim 1 wherein D is o-sulfo-phenyl, n and m are each 1, A is 2-methyl, B is 3-sulfo, the acylamino group is a 5-position substituent, R is cyclohexylene and Z is Beta -chloroethyl.
 6. The dyestuff of claim 1 wherein D is 3-sulfo-6-hydroxyphenyl, n and m are each 1, A is 2-ethyl, B is 5-sulfo, the acylamino group is a 3-position substituent, R is phenylene and Z is Beta -chloroethyl.
 7. The dyestuff of claim 1 wherein D is 2-sulfonaphthyl, n and m are each 1, A is 2-methoxy, B is 3-sulfo, the acylamino group is a 5-position substituent, R is propylene and Z is Beta -chloroethyl. 